Cerium oxidation state

Nd2-xCexCu04, 112,427-45 band structure schematic, 717 cerium oxidation state, 431 comparison with La2CuO>4 systems, 320 composition range, 437 copper oxidation state, 427,442 crystal chemistry, 428-31 crystal growth, 244,436-7,442-4... 

The X-ray structure showed a mean Ce-N bond length of 2.259 A the 0-0 distance of 1.328(6) A is indicative of a superoxide [O2] (rather than a peroxide [02] ), which implies that the cerium oxidation state is intermediate between +3 and +4. ... 

Originally, general methods of separation were based on small differences in the solubilities of their salts, for examples the nitrates, and a laborious series of fractional crystallisations had to be carried out to obtain the pure salts. In a few cases, individual lanthanides could be separated because they yielded oxidation states other than three. Thus the commonest lanthanide, cerium, exhibits oxidation states of h-3 and -t-4 hence oxidation of a mixture of lanthanide salts in alkaline solution with chlorine yields the soluble chlorates(I) of all the -1-3 lanthanides (which are not oxidised) but gives a precipitate of cerium(IV) hydroxide, Ce(OH)4, since this is too weak a base to form a chlorate(I). In some cases also, preferential reduction to the metal by sodium amalgam could be used to separate out individual lanthanides. 

Ln(II) in LnFj Ln(II) were determined after samples dissolution in H PO in the presence of a titrated solution of NFI VO, which excess was titrated with the Fe(II) salt. It was found that dissolution of the materials based on CeF CeFj in H PO does not change the oxidation state of cerium, thus phosphate complexes of Ce(III, IV) can be used for quantitative spectrophotometric determination of cerium valence forms. The contents of Ln(II, III) in Ln S LnS may be counted from results of the determination of total sulfur (determined gravimetric ally in BaSO form) and sum of the reducers - S and Ln(II) (determined by iodometric method). 

This method involves very simple and inexpensive equipment that could be set up m any laboratory [9, 10] The equipment consists of a 250-mL beaker (used as an external half-cell), two platinum foil electrodes, a glass tube with asbestos fiber sealed m the bottom (used as an internal half-cell), a microburet, a stirrer, and a portable potentiometer The asbestos fiber may be substituted with a membrane This method has been used to determine the fluoride ion concentration in many binary and complex fluondes and has been applied to unbuffered solutions from Willard-Winter distillation, to lon-exchange eluant, and to pyrohydrolysis distil lates obtained from oxygen-flask or tube combustions The solution concentrations range from 0 1 to 5 X 10 M This method is based on complexing by fluonde ions of one of the oxidation states of the redox couple, and the potential difference measured is that between the two half-cells Initially, each cell contains the same ratio of cerium(IV) and cerium(tll) ions... 

The principle just outhned has two parts. The first part deals with redox processes and was developed here by examining the relative stabihties of the -i-2 and -i-3 oxidation states of the lanthanides. It can be extended in a variety of ways. Thus if the f variation is shifted one element to the right, it tells us the nature of the f variations, and accounts for the distribution of the -i-4 oxidation states of the lanthanides [2, 10, 15]. Their stability shows maxima at cerium(IV) and terbium(IV), decreasing rapidly as one moves from these elements across the series. 

The +4 oxidation state is most stable at thorium, which lies beneath cerium. 

The reaction between Co(III) and Ce(III) has been the subject of a detailed study in a series of papers by Sutcliffe and Weber . Of particular value is the thorough investigation of the influence of anions on the rate in perchlorate media. The reaction was followed by measuring the disappearance of Co(IIl) at its absorption maximum of 650 m/i, a wavelength where both oxidation states of cerium are transparent and Co(II) absorbs only slightly. Changes in temperature and ionic strength affect the spectrum of Ce(III) at the 296 m/i maximum, but the... 

Belouzov-Zhabotinsky reaction [12, 13] This chemical reaction is a classical example of non-equilibrium thermodynamics, forming a nonlinear chemical oscillator [14]. Redox-active metal ions with more than one stable oxidation state (e.g., cerium, ruthenium) are reduced by an organic acid (e.g., malonic acid) and re-oxidized by bromate forming temporal or spatial patterns of metal ion concentration in either oxidation state. This is a self-organized structure, because the reaction is not dominated by equilibrium thermodynamic behavior. The reaction is far from equilibrium and remains so for a significant length of time. Finally,... 

The lanthanides are congeners of the Group IIIA metals scandium and yttrium, with the +3 oxidation state usually being the most stable. These ions are strong oxyphilic Lewis acids and catalyze carbonyl addition reactions by a number of nucleophiles. Recent years have seen the development of synthetic procedures involving lanthanide metals, especially cerium.195 In the synthetic context, organocerium... 

Depending on the electronegativity and the cation s oxidation state, the oxide can be either acidic or basic. Also, doping the ceria lattice does not automatically mean a substitution of a host cerium cation. Inomata and coworkers showed, in the case of Ce(i x)FexOy, that Fe3+ ions were located not only at Ce4+ sites, but also at interstitial sites (49). These interstitial ions bring about an increased barrier for electrons moving between Ce3+ and Ce4+, and influence the redox potential and the ease of reducibility of the material. 

A predominant feature of the atomic structure of the lanthanide group is the sequential addition of 14 electrons to the 4f subshell (Table 1). The /"electrons do not participate in bond formation and in ordinary aqueous solutions all of the lanthanides exhibit a principal (III) state. The common (III) state confers a similarity in chemical properties to all lanthanide elements. Some of the lanthanides can also exist in the (II) state (Nd, Sm, Eu, Tm, Yh) or in the (IV) state (Ce, Pr, Nd, Tb, Dy). Except for Ce(IV), Eu(II), and Yb(II), these unusual lanthanide oxidation states can only be prepared under drastic redox pressure and temperature conditions, and they are not stable in aqueous solutions. Cerium (IV) is a strong oxidizing agent... 

To generate 8O3 in acidic mediums, the reaction between sodium hydrogen sulfite and cerium ammonium nitrate should be employed. In (NH4)2Ce(N03)g, cerinm has 4+ oxidation state. In acidic mediums, (NH4)2Ce" +(N03)g easily oxidates the sulfite ion + 803 —> +... 

The compound cerium oxide (either Ce Oj or CeO ) is used to coat the inside of ovens because it was discovered that food cannot stick to oven walls that are coated with cerium oxide. Cerium compounds are used as electrodes in high-intensity lamps and film projectors used by the motion picture industry. Cerium is also used in the manufacturing and polishing of high-refraction lenses for cameras and telescopes and in the manufacture of incandescent lantern mantles. It additionally acts as a chemical reagent, a misch metal, and a chemical catalyst. Cerium halides are an important component of the textile and photographic industries, as an additive to other metals, and in automobile catalytic converters. Cerium is also used as an alloy to make special steel for jet engines, solid-state instruments, and rocket propellants. 

There are two oxides of cerium with oxidation states of 3 and 4. Cerium can also react with fiuorine and chlorine. 

The chemical properties of berkehum are rare earth-like character because of its half-filled 5/ subsheU and should be simdar to cerium. The element readily oxidizes to berkelium dioxide, Bk02 when heated to elevated temperatures (500°C). In aqueous solutions, the most common oxidation state is -i-3 which may undergo further oxidation to +4 state. A few compounds have been synthesized, the structures of which have been determined by x-ray diffraction methods. These include the dioxide, Bk02 sesquioxide, Bk203 fluoride,... 

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